Metal-Free and Additive-Free Synthesis of Imides and Nitriles from Ketones via Oxidative Cleavage of C(O)–C Bonds

The development of metal-free catalytic systems is highly desirable in organic transformation. Herein, a biomass-derived carbon catalyst with a high surface area was discovered to be robust for the metal-free and additive-free synthesis of cyclic imides and nitriles from ketones via the strategy of oxidative cleavage of C­(O)–C bonds for the first time, which remains a kind of challenging organic transformation even for metal catalysts. Experimental data and DFT calculations revealed that both the defective sites and surface oxygen-functional groups, particularly, the carboxylic acid groups in the carbon catalyst, were important for this transformation in which the defective sites activated O2 to generate the reactive oxygen species and the oxygen-containing functional groups facilitated the adsorption and activation of ketones on the catalyst surface to improve the catalytic efficiency. A plausible reaction mechanism was proposed for the oxidative transformation of ketones into imides and nitriles over the carbon catalyst.